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By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By R. A. Morse, P. M. Bridges, L. E. Wilsey, Howard N. Hall, P. L. Terwilliger

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By L. E. Wilsey, R. A. Morse, P. L. Terwilliger, Howard N. Hall, P. M. Bridges

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By V. V. Valleroy, A. J. Cornelius, B. T. Willman, G. W. Runberg, L. W. Powers

This paper reports the results of an investigation into the use of steam as a recovery agent. High oil recoveries by steam, as much as 100 per cent greater than by water flood, were demonstrated in laboratory linear cores. The principal mechanisms responsible for the additional oil have been identified as (1) thermal expansion of the oil, (2) viscosity reduction and (3) steam distillation. Although the first two also enhance recovery by hot water flood, they are effective with steam injection at lower volumes of produced fluids. Steam-zone residual oil saturation is independent of initial saturation. Recovery by steam is greater for lighter oils because they contain a greater fraction of steam-distillable components. Equations for the steam-zone advance in a radial homogeneous system are presented; these show the effect of reservoir parameters. The displacement in the hot liquid region moving ahead of the steam front can be estimated by a calculative procedure which is suggested. The method which takes account of the temperature gradient is applicable also to a regullar hot water flood. INTRODUCTION Considerable industry interest in the application of heat to petroleum reservoirs as a means of increasing oil recovery has been evident in the past few years. Three thermal methods which have attracted interest are (1) the injection of saturated steam, (2) the injection of hot water and (3) the injection of air into a formation to support combustion within the reservoir. Much has been published in recent years on underground burning, and there have been several papers on hot water injection. Although there are several early reports1,2 on steam injection, no recent experimental studies have been published on this recovery method. In our early thermal methods research, a marked improvement was found in oil recovery by steam injection compared with recovery by water injection in the same system. An investigation subsequently was undertaken to obtain quantitative information from which to evaluate steam injection as an oil recovery method. In addition, it was desired to investigate the recovery mechanism of hot water as compared with that of "cold" water and steam injection. An understanding of the mechanisms by which these processes operate would generally define favorable field conditions for their successful application. This paper reports the results of the laboratory study and suggests calculative approaches to estimate the field behavior of the steam-injection process. EXPERIMENTAL METHOD EQUIPMENT A schematic diagram of the equipment used for the displacement tests is shown in Fig. 1. Essentially, it consisted of a core with suitable means for recording temperatures, a feed system for injecting steam or cold or hot water, and a receiving train for condensing, cooling and measuring produced fluids. For the steam experiments, air-free saturated steam was piped from the boiler to the core face in insulated lines that were provided with steam traps and bleeds to remove any condensate formed in the lines due to heat losses. A 12-in. section of the line immediately ahead of

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.' Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer's3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

By H. W. Hitzrot

SEPARATING a mixture of particle sizes of material suspended in a liquid medium is by no means an exact science. Selecting machines for individual classifying operations is even more difficult. The plant operator's own background is of course invaluable, and considerable help may be obtained from technical articles, talks with sales engineers, and handbooks on ore dressing. These several sources of information, however, are difficult to marshal in proper perspective for the major decision on classification units that an operator may be called upon to make. To the present writer's knowledge this assembly of facts is not available in handbooks, and technical papers are scarce on classification equipment developed in the past five or six years. It is believed that this paper will be helpful to users of classification equipment at this particular period in the development of hydro-classification. For easy reference the following classification units now available and in use in metallurgical and industrial operations are listed below, with a brief description of each. Unit-type classifiers, bowl classifiers, and bowl desiltors are all rectangular tanks, slightly tilted, with reciprocating rakes or screws to remove settled sands. The unit-type classifier, Figs. 1 and 2, is available in widths from 14 in. to 20 ft and lengths up to 40 ft. The shallow bowl of the bowl classifier, Fig. 3, equipped with rotating rakes, is superimposed on the lower end of the tank. Reciprocating rake compartments for this design range from 18 in. to 20 ft wide. Bowl diameters vary from 4 to 28 ft. The flat-bottomed bowl of the desiltor, Fig. 4, of relatively large diameter, is equipped with rakes rotating outward and partly over a pit, which is created by extension of the rectangular tank into and under the bowl section. Bowl desiltors are available with reciprocating rake sections 4 to 20 ft wide and bowls from 20 to 50 ft in diam. The bowl desiltor is used for applications beyond the range of the bowl classifier. The hydroseparator, Figs. 5 and 6, is a circular tank equipped with slowly rotating rake arms, set on a slope, with interrupted rake or spiral blades to move the settled solids to a central discharge cone. Tank diameters vary from 4 to 250 ft. Tank depths at center are 2 to 3 ft for small units and up to 25 ft for larger units. Hydraulic classifiers of the sizer and super-sorter types, Figs. 7 and 8, are narrow, deep, rectangular tanks divided by vertical baffles into a series of pockets. Hydraulic water is added near the bottom of each pocket. Perforated constriction plates, spiral flow arrangements, or jets are used to disseminate the water under pressure (hydraulic water) throughout the bed of material in the pocket. Discharge valves on each pocket are operated automatically by a pneumatic mechanism, a pincer-type mechanism, or a pressure control and motor combination actuated by a hydrostatic tube within the pocket. Hydraulic classifiers are available in 4, 5, 6, and 8-pocket units of varying constriction plate areas to suit conditions. There is now a jet sizer of unit pocket design that can be made up in 1 to 25 sections or more to accommodate sizing requirements. The hydroscillator, Fig. 9, is a rectangular tank set on a slope of 3 to 4 in. per ft. A bowl is superimposed on the lower end. The bowl bottom is an oscillating rubber-covered disk, perforated to allow hydraulic water introduced beneath the disk to set up a teeter bed and thus produce an oversize or rake product exceptionally free of slimes, and material minus the mesh of separation. A shallow dam at the periphery of the bowl allows the coarse or oversize fraction to spill over and drop down into the tank compartment, where it is moved up the deck by reciprocating rakes. The material, minus the mesh of separation, overflows a circular and stationary weir which is several inches higher than the dam on the oscillating disk. It is carried off in a circular launder in the usual manner. These units are available in bowl diameters from 4 to 14 ft and with reciprocating rake compartment widths to suit the tons per hour to be handled. Centrifugal classifiers include the solid bowl centrifuge and the cyclone classifier. The solid bowl centrifuge, Fig. 10, consists of a truncated cone fixed to a horizontal shaft and rotating at high speed. An internal spiral rotating at slightly less speed continuously removes solids deposited on the inner surface of the cone, or bowl. Feed enters the cone by means of the hollow center shaft. Overflow leaves through ports at the large end of the cone, and oversize solids, moved by the spiral, exit through ports at the small end. Centrifugal classifiers of this type are available in cone diameters from 18 to 54 in. The cyclone classifier, Fig. 11, is a stationary cone having a cylindrical upper section and a lower cone section. Feed is introduced tangentially into the upper cylindrical section under pressure from a hydrostatic head or by means of a pump. Centrifugal force thus induced effects a classification within the cone, the fine sizes being carried off in the overflow through an opening at the top of the cylindrical section. Coarse solids at relatively high pulp density exit through a control valve at the apex of the lower cone section. Cyclone classifiers are available in 3, 6, 12, 14, 24, and 30-in. diam. The cone classifier, Fig. 12, is a steel-plate cone with sides usually about 60" from horizontal. It contains no rotating mechanism. Feed enters a feed-well at center and classification is effected by gravity and pulp density. Fines are carried off in the flow over a peripheral weir at the top of the cone. Settled solids exit through an opening at the apex. An apex valve actuated through levers and rods by the pulp density in the lower cone section is usually supplied. Diameters are usually maximum at 8 ft.

Jan 1, 1955

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60' bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By Oliver M. W. Sprague

THIS gold problem is full of complications and can hardly be handled adequately or comprehensively in any short period of time. Perhaps I might begin by mentioning a few aspects of the subject about which I suppose there will be no disagreement. The first of these is that we already have a stock of monetary gold in the United States far in excess of what is needed to support any desirable increase in the present volume of currency and credit. The second is that this already superabundant gold stock is certain to be considerably enlarged during the course of the war, and presumably during the months of readjustment following its conclusion. Some billions of additional gold, we may reasonably presume, will come into the country during these next few years, thus increasing the aggregate monetary gold stock from the present eighteen billions to perhaps twenty- two or even twenty-five billion dollars.

Jan 1, 1940

By G. Meyrick, H. W. Paxton

Observations on the tensile deformation of single crystals of austenitic stainless steels as a function of composition, orientation, and temperature are described and compared with relevant data for other alloys. Crystals free from second phases show sharp yield points followed by Lüders' extensions of up to 20 pct. The critical resolved shear stress is strongly temperature-dependent increasing fourfold between 423O and 77°K. A temperature-independent low rate of hardening follows the Luders' extension and is frequently associated with overshoot. Unlike pure metals where Proficse cross slip usually occurs at the end of linear hardening, this stage is terminated either by cross slip or by slip on the conjugate system, the particular node apparently depending upon initial orientation and composition. The presence of 6 ferrite or martensite has a profound effect upon the magnitude of the yield stress and the shape of the stress-strain curve. In experiments on transgranular-stress corrosion cracking of austenitic stainless steels in boiling magnesium chloride, several workers1'2 have shown that increasing amounts of nickel tend to reduce the probability of specimen failure. Reed and paxton3 have observed in single crystals that the macroscopic crack plane changes as the nickel content is increased. For 18 pct Cr-8 pct Ni, the crack plane is sensibly perpendicular to the applied tensile stress; for 20 pct Cr-20 pct Ni the crack plane is (100). The average crack-propagation speed is much lower in the 20 pct Ni crystals. Furthermore, the possible importance of stack-ing-fault energy in nucleation and growth of cracks has been suggested by a number of workers. While the general effect of variations in stack ing-fault energy appears to be quite well-correlated with observed variations in cracking characteristics, each of the theories assigns rather different detailed reasons for these effects. Because the stack ing-fault energy of austenitic steels is believed to be increased with increasing nickel content, and because some theories of trans-granular cracking postulate a mechanical stage in the crack propagation (rather than relying entirely on electrochemical solution), it appeared to be of some interest to investigate the mechanical properties of a series of different compositions of aus-tenite single crystals. These experiments were considered of intrinsic value in view of the relative scarcity of such data on fcc alloys. This paper gives the results of some experiments carried out with this aim in mind, and suggests various 'other experiments which may be helpful in future studies. The experiments are also of interest in view of the recent interest in obtaining higher-strength steels by control of the imperfection content of austenite; although the compositions are not directly comparable, the results are still probably valuable. Comparisons with experiments on other fcc alloy crystals are made where possible to see how well the general pattern of behavior is understood. EXPERIMENTAL PROCEDURE The alloys used in this investigation were vacuum-melted heats of nominally 20 pet Cr-20 pet Ni-60 pet Fe, 20pctCr-16 pct Ni-64 pct Fe, and 20 pctCr-12 pet Ni-68 pet Fe.* Analyses of the material are

Jan 1, 1964

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,' on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By M. E. Wadswort, A. S. Peck

Infrared data disclose that phenacite reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. The absorption band characteristic of the antisymmetrical C = 0 oleate structure appears at a spectral wavelength of 1623 cm-'. Chemisorption also results in the displacement of OH- and silicate from the mineral surface. Infrared absorbance at 1623 cm-1 is correlated with float-ability at different pH for -60-mesh phenacite particles. Phenacite, Be2SiO4, is an ore mineral often associated with quartz, microcline, and chrysoberyl in pegmatites and mica schist. Experimental phenacite beneficiating processes have been confined principally to the flotation of low grade ores occur-ing in several mountain ranges of Utah and Nevada. The U.S. Bureau of Mines ' has recently reported on the separation of phenacite from ore deposits of Mount Wheeler, Nev. Infrared techniques were previously applied by the authors to characterize the role of sodium oleate and oleic acid in the flotation of several non-sulfide minerals.23 A parallel study was projected to the flotation of the orthosilicate mineral phenacite with oleic acid. Infrared spectra provided a 'molecular fingerprint' of the mineral surface and permitted identification of the reaction mechanisms. Infrared data were complemented with flotation and chemical tests. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation, for which data are presented in graphical or spectral form, are described in chronological test order. Phenacite crystals from Mt. Antero, Colo., were obtained from Ward's Co., Monterey, Calif. The crystals were fragmented in a porcelain mortar to -60 mesh and then pretreated with 0.5 molar HC1 for 15 min to remove iron. Then, the mineral particles were washed free of acid with distilled water and dried. Part of the dried material was ground to a fine powder with a Fisher Grinder using an agate mortar and pestle. Next, the powder was placed in a graduated cylinder and mixed with 500 ml of distilled water. The mineral in suspension was decanted from the settled fraction after 5 min, and the colloidal suspension was used for adsorption tests in which a high specific mineral surface area was required for adsorption and infrared analysis. Conditioning was performed in 50 ml glass centrifuge tubes for both infrared and flotation test determinations. Twenty ml of colloidal suspension was used for the infrared adsorption tests. One and a half g of deslimed -60-mesh HCl pretreated phenacite was added to 20 ml of distilled water for flotation conditioning tests. Six mg of oleic acid was used for each infrared adsorption test, and 0.2 mg of oleic acid was used for the flotation conditioning tests. HCl and NaOH were used for pH modification. The pulps were stirred at a speed of about 1500 rpm for 3 min. Then, the solids were separated out and either dried at 50°C or immediately transferred to a float cell. The pH of the residual liquid was determined with a Beckman Zeromatic pH meter. The flotation procedure is described as follows: 1) A 325-1111 glass micro-float cell was filled with distilled water. 2) Conditioned mineral was placed in the cell and the pulp was aerated through the glass fritted bottom at 7 psi pressure. 3) Floated mineral was skimmed from the cell with a glass slide until flotation ceased. (The end point was reached in all tests in less than 2 min.) 4) The flotation products were dried, weighed, and the recovery was calculated. Samples for infrared analysis were made into mulls using either oleic acid or series 13-21 Halocarbon oil obtained from Halocarbon Products Corp., Hacken-sack, N.J. The mulls were placed between two sodium chloride windows. A characteristic phenacite infrared band at 1868 cm-' was used as an internal standard for quantitative determinations in which absorbance at this position was quantified by the baseline-tangent method4 and related to absorbance at 1623 cm-'. The ratio obtained by dividing absorbance at 1623 cm-' by absorbance at 1868 cm-' was defined as an absorbance quotient for use in graphical presentation.

Jan 1, 1968

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By P. R. PaeIay, A. Slibar

Using three-dimensional, stress-deformation rate equations for a Bingham plastic, an approximate solution for the laminar flow of drilling mud between the drill pipe and casing is given for the case when the velocity gradients due to axial flow are large compared to velocity gradients due to rotation. INTRODUCTION The fact that drilling mud can be treated, to a first approximation, as a Bingham plastic has been established by several investigators12,3,4,5. A Bingham plastic is a material that is rigid until a certain combination of stresses exceeds a critical value. When the stresses are sufficiently high to initiate flow, the reduced stresses have a constant ratio to the corresponding deformation rates at each point. Prediction of pressure and torque requirements to produce the desired flow of the material have been made by analytical solutions due to Bingham6, Reiner7, and Buckingham8. One part of the present means of calculation that requires clarification is the flow between the drill pipe and casing. Present methods treat the flow resulting from the rotation of the drill pipe separate from the flow produced by the axial pressure gradient. Since the non-linear behavior of a Bingham plastic implies that solutions cannot be superposed, the present analytical investigation was undertaken to obtain a solution to the problem of combined axial and tangential flow. Equations have been proposed for the three-dimensional flow of a Bingham plastic9,10,11 and it has been shown that the proposed equations lead to the usual solutions from the one-dimensional theory". Applying these equations to the flow between two concentric cylinders the problem of axial flow only13 and tangential flow only12 have been solved. In addition to the separate problems of axial and tangential flow between concentric cylinders, the authors have determined the relationship between external torque on the inside cylinder and axial pressure gradient necessary to initiate flow". The solution given in Ref. 14 points out the complexity of the present problem. The problem considered here is the case of simultaneous axial and tangential flow. The axial flow, necessary to keep the drill bit free of removed material, results from the axial pressure gradient. Tangential flow is present since the drill pipe rotates in the hole. The solution given here is valid when the shear stresses in the drilling mud due to rotation are small compared to the shear stresses resulting from the axial flow. This case for laminar flow can be encountered in oilfield drilling. STRESS-DEFORMATION RATE EQUATIONS A detailed derivation of the equations governing the behavior of a Bingham plastic is given in Ref. 10. This section briefly outlines the physical reasoning leading to this three-dimensional formulation of the stress-deforma-tion rate law. Experiments on a certain class of materials have demonstrated the following properties: (1) when a certain combination of the stresses is below a critical value no deformation of the material occurs, (2) to a first approximation this combination of stresses is independent of the hydrostatic pressure (negative average normal stress), (3) if flow occurs the ratio of the reduced stress to the corresponding deformation rate is constant at each point of the flowing material, and (4) incom-pressibility. For the one dimensional case of shear deformation, Bingham6 formulated the governing equation as dxx, = 0 for sxx < to and µdxx = s xx = to for sxx to , . where dxx is the shear deformation rate, sxx the shear stress, to the critical shear stress, and p the slope of the sxx vs dxx curve for dxx > 0. Fig. 1 shows the behavior for pure shear between two parallel plates. Taking into account the physical properties given above and assuming the critical combination of stresses to be measured by the octahedral shear stress, the fol-lowing three-dimensional equations have been proposed.

Jan 1, 1958

By J. W. Rutter, K. T. Aust

The migration of individual, large-angle grain boundaries has been studied as a function of tempereature and solute concentration in specimens of zone i.e filled lead containig very small additions of silver and of gold. Tile results are compared with various the-ories of grain boundary migration and with observations made prev.iorlsly of grain boundary migration in similar specimens of zone-refined lead containing tin additions. A previous investigation by the authors dealt with [he temperature dependence of grain boundary migration in bicrystals of zone-refined lead containing small additions of tin.&apos; It was shown that tin additions as low as a few parts per million cause a large decrease in the grain boundary migration rate at any given temperature, as well as a marked increase in the temperature dependence of the migration rate. It was found that existing theories of grain boundary migration. based on the motion of dislocations. or upon the concept of atom transfer in groups across the boundary (group process theory). or upon the control of grain boundary motion by volume diffusion of impurity atonls along with the boundary. are incapable of accounting for the observations. The single process theory of grain boundary migration. which is an absolute reaction rate calculation based on the transfer ui atoms singly across the moving boundary, was found to predict the migration rate reasonably well for a number of boundaries whose motion was shown to be very little influenced by impurities, but not for boundaries whose illation was influenced markedly by impurities. It was concluded that the elementary process of grain boundary migration involves the activation of single atoms during transfer across the boundary. and that inadequate knowledge is available to permit the influence of impurities to be properly taken into account. The present study was initiated to check the validity of the above conclusions with other alloy systems, namely high-purity lead with small additions of silver and of gold. Both silver and gold diffuse faster. and with a lower activation energy of volume diffusion. than does tin in lead;&apos; consequently, a study of the effects of silver and gold on grain boundary migration in high-purity lead offered a means of testing theories of boundary migration based on bulk diffusion of the solute (eg. ref. 3). In addition. it was hoped that the present work, in comparison with the results for tin in lead, would provide information concerning which factors are important in determin- ing the interaction between solute atoms and a grain boundary. EXPERIMENTAL PROCEDURE The preparation of bicrystals of zone-refined lead, with various silver or gold additions, was identical to that previously described for the lead-tin alloys.&apos;&apos;4 Each bicrystal consisted of a striated crystal which was grown from the melt. and an adjacent striation-free crystal which was introduced by artificial nucleation and growth.&apos;&apos;4 The striation or lineage substructure in the melt-grown crystal provided the driving force for grain boundary migration. During the preparation of striated single crystals by growth from the melt, it was found that silver or gold concentrations as low as 2 or 3 ppm by atoms were sufficient to cause formation of the hexagonal cell structure. which is due to the presence of impurity, during freezing. This structure is revealed on the solid-liquid interface by decanting the liquid during freezing. The hexagonal cell structure was observed previously4 in zone-refined lead crystals with tin contents above approximately 200 ppm by atoms. These concentrations of silver, gold, or tin are in agreement with the predicted amounts required for cell formation in lead,5&apos;6 under the present conditions of freezing.4 The absence of cell structure at decanted interfaces, therefore, served as a useful indication that the silver or gold contents were less than 2 or 3 ppm by atoms in the specimens as grown. It was found that grain boundary migration occurred only very slowly when the solute content approached that necessary for cell formation. As a result, the present experiments were conducted with silver or gold additions less than 1 ppm by atoms. This impurity level is well within the solid solubility limits for silver and gold in lead.7 The annealing treatments, measurements of grain boundary velocities, and orientation determinations were carried out as described previously.&apos; However. each bicrystal was also chemically polished in a solution consisting of 8 parts glacial acetic acid and 2

Jan 1, 1961

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969

By Robert Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field.

Jan 1, 1935

By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation&apos;-&apos; despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By L. G. Huntley

Points out differences between the new, more liberal, law passed by the Colombian Congress and the law passed in 1919, gives a few facts about the pipe-line concession granted to a Canadian company, and tells of new drilling developments. PROBABLY the most important development in the Colombian oil situation during the past year was the passage by Congress of a new petroleum law, which went into effect Jan. 31, 1923. The principal points of interest in which this new law changes or improves the previous one are as follows: Law 120 of 1919 provided that one person or corporation could not acquire more than three exploitation zones. of 5000 ha. each, and royalties were based on a sliding scale, to wit: 6 per cent. royalty on lands 400 km., or more, from the ocean; 8 per cent. on lands 200 but not over 400 km. from the ocean, and 10 per cent. royalty on lands located less than 200 km. from the ocean. Rentals were fixed at 10 centavos per hectare for the first year; 20 centavos for the second year; 50 centavos, third year, and $1 (one peso) yearly thereafter. Under this law the term of the lease was fixed at 20 years and, at the discretion of the government, could be extended for 10 years additional. After the expiration of the lease and its corresponding extension, the machinery and other material placed upon the property would vest in the government. A bond of 20,000 pesos was also required of the lessee to guarantee faithful performance of his contract.

Jan 3, 1924